Process for the manufacture of a cobalt molybdate catalyst

ABSTRACT

1. IN A PROCESS FOR MAKING A COBALT MOLYBDATE CATALYST, WHEREIN COBALT MOLYBDATE IS PRECIPITATED FROM THE COMBINED AQUEOUS SOLUTIONS OF A COBALT SALT, OF A MOLYBDENUM COMPOUND AND OF AMMONIA AT A TEMPERATURE OF ABOUT 60* C. AND AT A PH OF AT MOST 7, THE RESULTING PRECIPITATE IS FILTERED OFF, WASHED AND DRIED AT A TEMPERATURE OF AT LEAST 100* C., THE RESULTING DRY COBALT MOLYBDATE IS HEATED FOR SEVERAL HOURS AT ELEVATED TEMPERATURES, GROUND, SHAPED AND THE RESULTING SHAPES OF COBALT MOLYBDATE ARE SINTERED FOR SEVERAL HOURS, THE IMPROVEMENT WHICH COMPRISES COMBINING AN AQUEOUS SOLUTION OF THE COBALT SALT WITH THAT OF THE MOLYBDENUM COMPOUND IN THE ATOMIC ARTIO OF CO:MO OF ABOUT 1.05:1; ESTABLISHING IN THE COMBINED SOLUTIONS A PH BETWEEN 3.8 AND 6.0; DRYING THE PRECIPITATE AT 110-170* C; HEATING THE DRY COBALT MOLYBDATE TO TEMPERATURES BETWEEN 250 AND 550* C.; AND SINTERING THE COBALT MOLYBDATE SHAPES AT TEMPERATURES BETWEEN 500 AND 700* C WITH THE RESULTANT FORMATION OF A COBALT MOLYBDATE CATALYST HAVING AN INNER SURFACE ARE BETWEEN 4 AND 8 SQUARE METERS/G. AND A VOLUME OF PORES BETWEEN 0.1 AND 0.2 MILLILITERS/G.

United States Patent m US. Cl. 252-470 5 Claims ABSTRACT OF THE DISCLOSURE Improved production of a cobalt molybdate catalyst, wherein cobalt molybdate is precipitated from the combined aqueous solutions of a cobalt salt, of a molybdenum compound and of ammonia at a temperature of about 60 C. and at a pH of at most 7, the resulting precipitate is filtered off, washed and dried at a temperature of at least 100 C., the resulting dry cobalt molybdate is heated for several hours at elevated temperatures, ground, shaped and the resulting shapes of cobalt molybdate are sintered for several hours. The improved production comprises more particularly combining the aqueous solution of the cobalt salt with that of the molybdenum compound in the atomic ratio of CozMo of about 1.05:1, establishing in the combined solutions a pH between 3.8 and 6.0; drying the precipitate at 1l0-l70 C.; heating the dry cobalt molybdate to temperatures between 250 and 550 C. and sintering the cobalt molybdate shapes at temperatures between 500 and 700 C. with the resultant formation of a cobalt molybdate catalyst having an inner surface area between 4 and 8 square meters/ g. and a volume of pores between 0.1 and 0.2 milliliters/g.

A process for making a cobalt molybdate catalyst has already been described in German published Specification Auslegeschrift 1,417,670, wherein cobalt molybdate is precipitated from the combined aqueous solutions of a cobalt salt, of a molybdenum compound and of ammonia at a temperature of about 60 C. and at a pH of at most 7, the resulting precipitate is filtered off, washed and dried at a temperature of at least 100 C., the dry cobalt molybdate is heated for several hours at elevated temperatures, ground, shaped and the resulting shapes of cobalt molybdate are sintered for several hours. Similar processes have been disclosed in German published Specification Offenlegungsschrift 1,418,750, in US. Pat. 2,625,519, and in German published Specification Auslegeschrift 1,184,- 326. This latter Specification is noted to indicate in column 3, line 14, a surface area between 16 and 17 square meters/ g. for the catalyst.

Cobalt molybdate catalysts find use in the gas phase oxidation, for example of propylene to give acrolein and acrylic acid, of acrolein to give acrylic acid, of butane and butene-Z to give maleic anhydride, and of propylene with ammonia to give acrylonitrile.

Cobalt molybdate catalysts have been produced heretofore by processes which have considerable disadvantages. More particularly, the catalysts so made have been found to either combine satisfactory hardness with minor selectivity or to combine satisfactory selectivity with poor resistance to abrasion. It should be added that the catalysts made by prior art methods become rapidly less active, are difficultly reproducible and are irregularly selective.

The present invention now provides a process for making cobalt molybdate catalysts, which combine good abrasion resistance with good selectivity and long service life, which process comprises combining the aqueous solution of the cobalt salt with that of the molybdenum compound in the atomic ratio of Co:Mo of about 1.05:1; establishing in the combined solutions a pH between 3.8 and 6.0; drying the precipitate at -170" C.; heating the dry cobalt molybdate to temperatures between 25 0 and 55 0 C., shaping the cobalt molybdate and sintering the shapes at temperatures between 500 and 700 C. with the resultant formation of a cobalt molybdate catalyst having an inner surface area between 4 and 8 square meters/ g. and a volume of pores between 0.1 and 0.2 milliliters/ g.

Further embodiments of the process of the present invention, which can be used singly or in combination, comprise:

(a) combining an aqueous solution of cobalt nitrate with and aqueous ammoniacal solution of ammonium molybdate;

(b) adjusting the pH to a value between 4.0 and 4.4;

(c) grinding the cobalt molybdate and then compressing it into pellets with the use of about 2-5 weight percent of graphtie as a pelleting auxiliary;

(d) sintering the shapes of cobalt molybdate so as to establish an inner surface area between 5 and 7 square meters/ g. in the resulting cobalt molybdate catalyst.

In the production of an active catalyst as described hereinabove, it is an important requirement for the catalyst to be precipitated from aqueous solutions containing Co and M0 in an atomic ratio of about 1.05:1. Using atomic ratios outside this range results in catalysts of impaired selectivity. In the processes first referred to hereinabove, use has been made of solutions containing Co and M0 in an atomic ratio of 1.00:1.00.

In accordance with this invention, it is also necessary for the precipitation to be effected exactly within the pH ranges between 3.8 and 6.0, preferably between 4.0 and 4.4, as this is critical for the structure, strength and reproducibility of the catalyst. The heat treatment, which should conveniently be effected over a period of 12-20 hours at 250 to 550 C., prior to the pelleting and sintering steps, has been found to improve the selectivity and resistance to abrasion of the catalyst. After transformation into pellets, the catalyst should be sintered over a preferred period of 6-10 hours at 500-700 C. so as to establish an inner BET-surface area between 4 and 8 square meters/g., preferably between 5 and 7 square meters/g, and a volume of pores between 0.1 and 0.2 milliliters/ g. By establishing an inner surface area within these narrow limits, it is possible to produce catalysts which combine optimum selectivity with a long service life and with the necessary hardness. Larger surface areas actually increase the castlysts activity (conversion of starting material, e.g. acrolein) but they reduce its hardness and selectivity. Smaller surface areas in turn cause inactivation of the catalyst. As will more clearly result particularly from comparative Examples 3 to 8 hereinafter, catalysts having less good overall properties were obtained in all those experiments which were carried out under conditions outside those specified in the present invention.

EXAMPLE 1.-Invention An ammoniacal solution of 384 g. of ammonium heptamolybdate (NH Mo O -4H O in 549 g. of water was added to a solution of 665 g. of cobalt nitrate CO(NO3) 2' in 648 g. of water, at 60 C. and at a pH between 4.2 and 4.4. This resulted in the precipitation of cobalt molybdate. The solutions used contained Co and M0 in an atomic ratio of 1.05:1. The precipitate was filtered off, washed with Water and dried at C. The dry cobalt molybdate was subjected to thermal treatment over 16 hours at 3 500 C. ground, admixed with 25 weight percent of graphite and compressed into pellets with the dimensions of 4 X 5 mm. The pellets so made were finally sintered for 8 hours at 600 C. and then had an inner surface area of 5.8 square meters/g. and a volume of pores of 0.15 milliliters/g.

200 milliliters of the cobalt molybdate catalyst so produced were placed in a reactor 1 m. long and 25 mm. Wide, which was heated by means of a salt bath. At a salt bath temperature of 375 C., the catalyst was supplied, per hour, with 27 normal liters (S.T.P.) of acrolein, 42 normal liters of oxygen, 345 normal liters of nitrogen and 105 normal liters of steam. The products coming from the reactor were condensed and the acrylic acid obtained was analyzed. 41 g./h. of acrylic acid were obtained. The acrolein conversion rate and the acrylic acid yield or selectivity were determined along the following formula:

Acrolein conversion rate (percent) Mols of acrolein used-mole of acrolein recovered Mols of acrolein used Acrylic acid yield or selectivity (percent) Mols of acrylic acid-100 Mols of acrolein converted EXAMPLE 2.Invention The catalyst was the same as that used in Example 1, save that it was sintered for 7 hours at 600 C., had an inner surface area of 6.6 square meters/ g. and a volume of pores of 0.15 milliliters/g. 34 liters of the catalyst were placed in a reactor comprising 34 tubular structures 2.50 meters long and 25 mm. wide. The reactor was heated by means of a salt bath.

At a salt bath temperature of 385 C., the catalyst was fed, per hour, with a mixture of 4.36 normal cubic meters of acrolein, 7.42 normal cubic meters of oxygen, 50 normal cubic meters of carbon monoxide/carbon dioxide and 10.9 normal cubic meters of steam. The resulting reaction products were water-washed and 7 480 g./hr. of acrylic acid were isolated therefrom, unreacted acrolein being recycled to the reactor, together with recycle gas. The acrolein conversion rate was 58% and acrylic acid was obtained in a yield (selectivity) of 90.5% The catalyst performance was 220 g. of acrylic acid per liter of catalyst per hour. After 6 months of operation, the activity of the catalyst could not be found to have been impaired.

The following Examples 3 to 8 are given for the purpose of comparison.

EXAMPLE 3 An atomic ratio of Co:Mo exactly of 1:1 (prior art) was established in the solutions. The starting material, which was a solution of 634 g. of cobalt nitrate in 648 g. of water, was admixed at 60 C. at a pH between 4.2 and 4.4 with an ammoniacal solution of 384 g. of ammonium heptamolybdate in 549 g. of water to effect precipitation. The precipitate was then treated in the manner described in Example 1.

The catalyst so made, which had a surface area of 6.5 square meters/g. and a volume of pores of 0.17 milliliters/g., enabled the production of 40.5 g./hr. of acrylic acid, for an acrolein conversion rate of 58%. This corre sponded to a selectivity of merely 79% for a catalyst performance of 203 g. of acrylic acid per liter of catalyst per hour.

EXAMPLE 4 The starting solutions contained Co and M0 in the atomic ratio of 1.1:1. Precipitation of the starting solu- 4 tion of 698 g. of cobalt nitrate in 648 g. of water was effected at 60 C. at a pH between 4.2 and 4.4 with the use of an ammoniacal solution of 384 g. of ammonium heptamolybdate in 549 g. of water. The resulting precipitate was then treated under the conditions reported in Example 1. The catalyst so made, which had a surface area of 6.2 square meters/g. and a volume of pores of 0.14 millililterslg, produced 37 g./hr. of acrylic acid, for an acrolein conversion rate of 54%. This corresponded to a selectivity of merely 77.5%, for a catalyst performance of 185 g. of acrylic acid per liter of catalyst per hour.

EXAMPLE 5 The procedure was the same as that described in Example 1, save that the ammoniacal solution of ammonium heptamolybdate was admixed with the quantity of ammonia necessary to effect precipitation at a pH higher than 6 up to 7. The catalyst, which was further treated in the manner described in Example 1, had a surface area of 6.7 square meters/g. and a volume of pores of 0.18 milliliters/g. As compared with the catalyst made in ac cordance with this invention, it was substantially less resistant to abrasion. This was demonstrated by the fact that the catalyst pellets were found to have been decomposed after a few days of operation. The catalyst produced 39 g./ hr. of acrylic acid for an acrolein conversion rate of 61%. This corresponded to a selectivity of 72.2% for a catalyst performance of 195 g. of acrylic acid per liter of catalyst per hour.

EXAMPLE 6 The procedure was the same as that described in Example 1, save that the ammoniacal ammonium heptamolybdate solution was admixed with the quantity of ammonia necessary to ensure precipitation at a pH of 3.5. The resulting catalyst, which was further treated in the manner described in Example 1, had a surface area of 5.6 square meters/g., a volume of pores of 0.16 milliliters/ g. and a minor resistance to abrasion. The catalyst produced 32 g./hr. of acrylic acid for an acrolein conversion rate of 46%. This corresponded to a selectivity of 78.6% for a catalyst performance of 160 g. of acrylic acid per liter of catalyst per hour.

EXAMPLE 7 The procedure was the same as that described in Example 1 save that the catalyst pellets were finally sintered over a period of merely 4 hrs. at 600 C. This gave a catalyst which had a surface area of 9.6 square meters/g. and a volume of pores of 0.25 milliliters/g. The catalyst so made had a mechanical strength lower than that of the catalysts made in Examples 1 and 2. The catalyst was tested in the manner described in Example 2 and found to produce 7 g./hr. of acrylic acid for an acrolein conversion rate of 60%. This corresponded to a selectivity of 82.9% for a catalyst performance of 209 g. of acrylic acid per liter of catalyst per hour. It was necessary for the test to be interrupted after as short a period as 18 days, as the catalyst was found to have been decomposed.

EXAMPLE 8 The procedure was the same as that described in Example 1, save that the catalyst pellets were finally sintered for 12.5 hours at 600 C. until the catalyst was found to have a surface area of 3.0 square meters/ g. and a volume of pores of 0.08 milliliters/g. Apart from its minor resistance to abrasion, the catalyst so made produced merely 14 g./hr. of acrylic acid for an acrolein conversion rate of 28%, under the conditions reported in Example 1. This corresponded to a selectivity of 56.6% for a catalyst performance of 70 g. of acrylic acid per liter of catalyst per hour.

The results obtained in Examples 1 to 8 are summarized in the following Table indicating that merely the catalysts prepared in accordance with this invention (Examples 1 TABLE 3. The process as claimed in claim 1, wherein the pH is adjusted to a value between 4.0 and 4.4.

Catalyst perfor- Selectivlty mance (g. acrylic Atomic ratio of BET-surface Volume of for acrylic acid per liter C:Moi 11 pH during area in pores in acid in of catalyst solutions precipitation sq.m.lg. .lg. percent per hour) What is claimed is:

1. In a process for making a cobalt molybdate catalyst, wherein cobalt molybdate is precipitated from the combined aqueous solutions of a cobalt salt, of a molybdenum compound and of ammonia at a temperature of about 60 C. and at a pH of at most 7, the resulting precipitate is filtered 01f, washed and dried at a temperature of at least 100 C., the resulting dry cobalt molybdate is heated for several hours at elevated temperatures, ground, shaped and the resulting shapes of cobalt molybdate are sintered for several hours, the improvement which comprises combining an aqueous solution of the cobalt salt with that of the molybdenum compound in the atomic artio of CozMo of about 1.05:1; establishing in the combined solutions a pH between 3.8 and 6.0; drying the precipitate at 110-170 C.; heating the dry cobalt molybdate to temperatures between 250 and 550 C.; and sintering the co balt mblybdate shapes at temperatures between 500 and 700 C with the resultant formation of a cobalt molybdate catalyst having an inner surface area between 4 and 8 square meters/g. and a volume of pores between 0.1 and 0.2 milliliters/ g.

2. The process as claimed in claim 1, wherein an aqueous solution of cobalt nitrate is combined with an aqueous ammoniacal solution of ammonium molybdate.

4. The process as claimed in claim 1, wherein the cobalt molybdate is ground and then compressed into pellets with the use of about 2-5 weight percent of graphite as a pelleting auxiliary.

5. The process as claimed in claim 1, wherein the cobalt molybdate shapes are sintered so as to establish an inner surface area between 5 and 7 square meters/ g. in the resulting cobalt molybdate catalyst.

DANIEL E. WYMAN, Primary Examiner A. P. DEMERS, Assistant Examiner US. Cl. X.R. 

1. IN A PROCESS FOR MAKING A COBALT MOLYBDATE CATALYST, WHEREIN COBALT MOLYBDATE IS PRECIPITATED FROM THE COMBINED AQUEOUS SOLUTIONS OF A COBALT SALT, OF A MOLYBDENUM COMPOUND AND OF AMMONIA AT A TEMPERATURE OF ABOUT 60* C. AND AT A PH OF AT MOST 7, THE RESULTING PRECIPITATE IS FILTERED OFF, WASHED AND DRIED AT A TEMPERATURE OF AT LEAST 100* C., THE RESULTING DRY COBALT MOLYBDATE IS HEATED FOR SEVERAL HOURS AT ELEVATED TEMPERATURES, GROUND, SHAPED AND THE RESULTING SHAPES OF COBALT MOLYBDATE ARE SINTERED FOR SEVERAL HOURS, THE IMPROVEMENT WHICH COMPRISES COMBINING AN AQUEOUS SOLUTION OF THE COBALT SALT WITH THAT OF THE MOLYBDENUM COMPOUND IN THE ATOMIC ARTIO OF CO:MO OF ABOUT 1.05:1; ESTABLISHING IN THE COMBINED SOLUTIONS A PH BETWEEN 3.8 AND 6.0; DRYING THE PRECIPITATE AT 110-170* C; HEATING THE DRY COBALT MOLYBDATE TO TEMPERATURES BETWEEN 250 AND 550* C.; AND SINTERING THE COBALT MOLYBDATE SHAPES AT TEMPERATURES BETWEEN 500 AND 700* C WITH THE RESULTANT FORMATION OF A COBALT MOLYBDATE CATALYST HAVING AN INNER SURFACE ARE BETWEEN 4 AND 8 SQUARE METERS/G. AND A VOLUME OF PORES BETWEEN 0.1 AND 0.2 MILLILITERS/G. 